Method for manufacture of cyclohexylphenols



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Patented. July 11, 1933 UNITED STATS EDGAR C. BRIT-TON AND RALPH P. PERKINS, 0F MIDLAND, MICHIGAN, ASSIGITORS T0 FATE FIG

THE DOW CHEMICAL COMPANY, OF MIDLAND, MIGAN, A CORPORATION OF MICEIGAJN METHOD FOR MANUFACTURE OF CYCLOHEXYLPHENOLS No Drawing.

The present invention concerns a method of making cyclohexylphenols from phenol and suitable cyclohexenic source-material. This application is a continuation in part of our prior application Serial No. 481,350, filed September 11, 1930.

We-have found that a D uol will react with a cyclohexene or the equivalent thereof such as a cyclohexanol, to form a product essentially comprising orthoand para-cyclohexylphenols as major products along with a relatively small fraction of a meta-cyclohexylphenol as a minor product provided that ortho-, meta-, and para-positions are unsubstituted in the phenol employed as a reac: tant so that said ortho-, meta-, and paraproducts may be formed. We further have found that said ortho compound can be converted into the corresponding para compound, and that by adding an ortho-cyclohexylphenol to the reaction mixture, the formation of additional ortho compound is substantially inhibited.

Our invention, then, consists of the method hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail several modes of carrying out our invention, such disclosed modes illustrating, however, but several of the various ways in which the principle of our invention may be used.

In carrying out our improved method, We react in a phenol with a cyclohexene or other suitable source material capable of yielding a cyclohexene, such as a cyolohexanol, in the presence of a suitable silicic catalyst, e. g. fullers earth or other bleaching earth, clay, silica gel, lonsil, or other siliceous material, with or without a solvent, whereby is obtained a product comprising essentially an ortho-cyclohexylphenol and a para-cyclohexylphenol, together with higher condensation products. lhe phenol preferably is present in excess, i. e. in approximately 1 to 10 times the theoretical amount, and the catalyst present in a quantity representing fronrabout l to 10 per cent of the weight of phenol employed. Such excess of phenol is desirable in that it tends to prevent Application filed Gctober 23,1931. Serial No. 570,654.

the formation of poly-cyclohexyl-substituted phenols,

The reactants may be mixedeither hot or cold. For instance, the phenol may be heated to the desired temperature and the cyclohexenic source-material added thereto in either hot or cold condition.

The reaction may be carried out at any temperature between 100 and 350 0 and under atmospheric or superatmospheric pressure. We have found that the relative proportions of orthoand para-cyclohexylphenol in the product vary according to the reaction temperature employed. The proportion of the para compound, in the mixture of cyclohexylphenol products, appears to be maximum when said compounds are formed at a reaction temperature above 160 C. or thereabout.

After substantial completion of the reaction, the crude reaction mixture is treated in any preferred way to separate the desired products therefrom. For instance, the crude product may be fractionally distilled to substantially separate the unreacted phenol,

,cyclohexylphenols, and other products, or

after the unrcacted phenol is removed by fractional distillation the remaining crude mixture may be separated into the components thereof by fractional crystallization from a suitable organic solvent. F or example, para-cyclohexylphenol may be recrystallized from benzene, toluene, chlorobenzene, ortho-diohlorobenzene, naphtha, etc, Whereas ortho-cyclohexylphenol may be recrystallized from solvents such as carbon Still antetrachloride or petroleum other. other mode of procedure is to remove the un reacted phenol, dissolve the residual mixture in aqueous sodium hydroxide solution and crystallize sodium para-cyclohexylphenate therefrom, which latter compound may then be converted into free para-cyclohexylphenol in any desired way. The residual solution which contains sodium ortho-cyclohexylphenate, may be acidified and the precipitate fractionally distilled to separate ortho-cyclohexylphenol therefrom. 7

Our invention may be carried out inany one of several ways. or instance,if theproc Nil ess is to be carried out to prepare para-cyclohexylphenol from henol and cyclohexene or source-material yie ding the latter, such components are reacted to obtain a product which may be fractionally distilled or otherwise treated to separate para-cyclohexylphenol therefrom, the other compounds, e. g. phenol, ortho-cyclohexylphenol, and cyclohexylphenyl other, it present, being returned to the process together with sufficient added )henol and cyclohexene or equivalent thcreoi By thus returning ortho-cyclohexylphenol to the process, the formation of additional ortho compound is substantially avoided, the final product comprising essentially para-cyclohoxylphenol accompanied by a relatively small amount of the corresponding ortho compound and tar. On the other hand, a similar addition of para-cyclohexylphenol to be mixed reactants (phenol and cyclohexene) does not appear to prevent the formation of additional para-eyclohexylphenol in usual amount.

Again, if it is desired to convert ortho cyclohexylphenol into the corresponding para-compound, the former is heated in the presence of at least one of the abovementioned catalysts with or without the presence of added phenol, preferably with agitation of the reaction mixture, under any suitable pressure, whether atmospheric, increased or reduced pressure, and at a temperature between approximately 17 5 and 350 0., thereby forming a mixture of the ortho and para compounds which may be separated into the constituents thereof. For instance, we have heated ortho-cyclohexylphenol together with phenol and Tonsil at about 200 C. for 5 hours as just described, then removed the catalyst from the crude reaction mixture, and

fractionally distilled the latter to obtain the-- mixed cyclohexylphenols which then were dissolved in about twice their volume of hot 15 per cent aqueous sodium hydroxide solution and cooled, whereby the sodium salt of the para compound crystallized therefrom. Para-cyelohexylphenol cannot, under conditions similar to those described above, be

converted to ortho-cyclohexylphenol to an appreciable extent.

The following examples illustrate several of the various modes of carrying out our invention E'wample 1 A reaction mixture, consisting of 1200 grams (15 moles) of cyclohexene, 5650 grams moles) of phenol, and 300 grams of fuller s earth, was heated in an iron bomb during an 8 hour period, the reaction temperature being grar'iually raised to 257 C. during the heating operation. The reaction mass was then removed from the bomb, filtered to remove fullers earth therefrom, and fractionally distilled. There was obhexene used. From the mixture of cyclohexylphenols there were subsequently separated 877 grams of para-cyclohexylphenol and 1307 grams of ortho-cyclohexylphenol,

both products being recovered as substan-' tially pure compounds.

Example 2 A reaction mixture consisting of 2500 grams (25 moles) of cyclohexanol 3760 rams (40 moles) of phenol, and 300 grams o Tonsil, was heated, during a 3 hour period, in an iron bomb, the temperature being increased gradually from 215 to 250 C. during the heating operation. The reaction mixture was then removed from the bomb, filtered to separate Tonsil therefrom, and fractionally distilled. There were obtained approximately 2215 grams of unreacted henol, 80 grams of a mixture consisting of? cyclohexylphenyl ether and ortho-cyclohexylphenol, 1600 grams of ortho-cyclohexylphenol, 900 grams of paracyclohexylphenol, and 650 ams of higher -condensation products. The total yield of cyclohexylphenols was approximately 67 per cent of theoretical, based on the quantity of cyclohexene used.

Example 3 A reaction mixturepconsisting of 750 grams (8 moles) of phenol and 40 grams of Tonsil was heated to 230 C..in an autoclave and 200 grams (2 moles) of cyclohexanol was added to the heated mixture. The mixture was maintained at 230 0., with stirring, during a 0.5 hour period. The reaction products were separated through rocedure similar to that described in Examp e 2, 543 grams of unreacted phenol, 280 grams of mixed orthoand paracyclohexylphenols, and 29 grams of higher condensation products being obtained thereby- The yield of cyclohexylphenols was approximately 80 per cent of theoretical, based on the quantity of cyclohexanol used.

Example 4 tion was found to contain aaproximately 77 grams of ortho-cyclohexylp enol and about 11 grams of the paraisomer. The yield of mixed cyclohexylphenols was 86 per cent of theoretical, based on the quantity of cyclohexene used.

otness Example 5 In a series of four condensotions of cycloliexene with phenol, the reactionjproduct obtained in each run was fractionally distilled to obtain para-cyclohexylphenol (B. P. 180- 182 C. at 25 mm. pressure) as the desired product. The fractions comlprising phenol, ortho-cyclohexylphenol (B. i68-170 C. et 25 mm.) and mixed ortho and para compounds (B. P; 170l80 C. et 25 mm.) were returned to the next reaction mixture to replace equivalent amounts of cyclohexene and phenol. The residual tar fraction was discorded.

The four runs were carried out in 4, 9, 6, and 8 hours, respectively, at o temperature of about 195-2l0 C.- The first run started with 5650 grams moles) of phenol and 1200 grams (15 moles) of cyclohexene, The crude reaction product ohteined thereby, was irsctionelly distilled, yielding approximately 4250 grams of phenol, 1000 grams of orthocyclohexylphenol, 1350 grams of pore-cyclohexylphenol, and 200 grams of ten The charge for the second run consisted of the The ortho and pars compounds were obtained in 1 2 per cent end 71 per cent yields, respectively, hosed on the cyclohenene, the total yield of cycloherylphenols losing epproximotely per cent. By continuing the proc .ess, the yield of pore compound accordingly will approach more closely to the totsl yield of cyclohexylphenols.

A mixture, consisting of 210 groans oi phenol, 7 1.5 grams of l -methyl-cyclohexene, and 10.5 grams of Tonsil, was maintained st between 105 and 145 C. during" e hour period. The reaction mass was frectionolly distilled, l5 gramsoi unreocted l-methyl-cy clohexene, 1-61 grams of phenol, greens of nearly pure p-(l-methyl-cyclohexyl) phenol, end 14 grams of e tarry residue being ohtsined thereby. The yield-oi" p- (l-methyl-cy- V clohexyl) -phenol was approximately 805 per.

cent oi theoretical, based upon the quantity of l-methyl-cyclohexene employed and not recovered as unreacted materiel.

Ewawtple 7 A mixture, consisting of 225 grams of ortho-cresol, 57 grams of cyclohexene, and 11 grains of Tonsil was hosted, in on iron bomb, at between 190 and 205 C. during a 2.5 hour period. The reaction mass was filtered and then fructionelly distilled, 150 grams of unreact'ed ortho-cresol, 116 grams of e mixture ofcyclohexylcresols, and 12 grams of u terry residue lacing obtained thereby. Upon crystallization of the cyclohexylcresol mixture from solvent naphtha there was isolated p-cyclohexyl-o-cresol, of melting point 7 8 to 785 10. and of looiling point 180 to 181 C. at 25 millimeters pres sure.

When preparing cyclohexylphenols "from phenol and cyclohexene or cyclohexonol according to. our method, it relatively small fraction of meta-cyclohexylphenol is formed along" with its orthoand pare-isomers as major products. Metu-cyclohcxylphenol may be separated from the mixture of the some isomeric compounds by froctionally distilling saiid mixture so osto remove most of the ortho-cycloherrylphenol therefrom, converting the metuand pers-cyclohexyldimn pern-cyclohexylphenute through froctionnl crystallization of said sodium salts from Water, acidifying the sodium metecyclohexylphenate fraction to liloerzite metecyclohexylphenol, end purifying the letter through recrystellizetion from on organic solvent, e. g. petroleum ether. Purified ineto-cyclohexylphenol, which is ohtnined as fine White needles, melts at approximately 54 to 55 6. and boils st oppronimetely 180 J. under 25 millimeters of pressure. l/Vhen preparing cyclohexylphenols oecording to our improved method, mete-cyclohexylphenol'is generally formed in on amount repre senting from. 1 to 5 per cent of the Weight of the mixed cyclohexylphenol products.

While We mey "form cyclohexylphenols by reacting o phenol with e cyclohexene or equivalent thereoil in the presence oi? c. siliceous cotalystot cny temperoture hetvveen end 350 (3., Wepreler to corry the reaction out at o temperetnre between 175 phermls to their sodium salts, separating soioo and 350 C. At tempereturcs helovv 175 C.

some intermediate products, such es cycloherrylphenyl other ore sometimes olotoined. When the reaction is curried out at tempers tures between 175 end 350 C. such interrec mediate products are largely converted into cyclohexylphenols.

. We do not limit our invention to the specific reection components 'rnenticned in the example. For instonce, phenols, containing noreective groups other then the hydroxyl group (6. g. the various oresol elkyl, elkony,

arylcx end orellrony substituted phenols,

. phony phenols, etc), in general, mey be re acted with cyclohexene cyclohexanol, or suitable derivatives thereof, such as the hydro-.

carbon derivatives thereof, e. g. methyl cyclohexene, or methylcyclohexanol, as a ove described.

In summary, the present invention comprises:

(a) Reacting a phenol with cyclohexcne or equivalent thereof, at a temperature between 100 and 350 C. and in the presence of a siliceous catalyst, to form a cyclohexylphenol; I

(bl lteacting a phenol, having the general formula wherein X represents hydrogen or a substituent selected from the group consisting of hydrocarbon, alkorry aryloxy, or aralkoxy substituents, with eyclohexene or equivalent thereof, under reaction conditions similar to those described in (0;), to form orthoand para-cyclohexylphenols conjointly;

(c) When operating according to procedure similar to that described in (1)), adding the ortho-cyolohexylphenol compound, which is generally formed as a product from the reaction involved, to the reaction mixture to promote the formation of a para-cyclohexylphenol and inhibit the further :tormation of a ortho-cyclohexylphenol; i

(d) Reacting phenol with cyclohexene or equivalent thereof at a temperature between 100 and 350 C. to form ortho-cyclohexylm in which the reaction is carried out.

phenol and its Inetaand para-isomers con- ]ointly.

By the expression cyclohexenic sourcematerial as used in the specification and claims, we mean a cyclohexene or other compound capable of yieldinga cyclohexene, under the conditions in which the reaction is carried out, to react with the phenolic compound. Similarly, the expression cyc1o 'hexene source-material shall be understood to mean cyclohexene or a compound capable of forming cyclohexene under the conditions Other modes of applying the principle of ,Olll invention may be employed instead of phenol with a cyclohexenic source-material at a temperature between 100 and 350 C. and in the presence of a siliceous catalyst.

3. The method of making a cyclohexylphe- 1101, which comprises reacting a monohydric phenol with a cyclohexenic source-material under superatnmsphoric pressure, at a temperature between 100 and 350 C. and in the presence of a siliceous catalyst.

4. The method of mal-iing a cyolohexylphenol, which comprises reacting a monohydric phenol with a cyclohexenic source-material, under superatmospheric pressure, at a temperature between 175 and 350 C. and in the presence of a siliceous catalyst.

5. The method of making an ortho-cyclohexylphenol and its para-isomer conjointly,

which comprises reacting a phenol, having the general formula;

wherein X represents hydrogen or a substituent selected from the group consisting of hydrocarbon, alkoxy, aryloxy, and aralkoxy substituents, with a cycloheXcnic source-material in the presence of a silceous catalyst.

0. The method of making an ortho-cyclohexylphenol and its para-isomer conjointly, which comprises reacting a phenol, having the general formula;

wherein X represents hydrogen or a substituent selected from the group consisting of hydrocarbon, alkoxy, aryloxy and aralkoxy substituents, with a cyclohexenic source-material, under superatmospheric pressure, at.

a temperature between 175 and 350 C. and in the presence of a siliceous catalyst.

8. The method of making orthoand paracyclohexylphenols conjointly, which comprises reacting phenol with a cyclohexene Lie phenol, her in presence of e siliceous phenol and cyclohexeiie source-materiel in e,"

znolecular ratio between 1 to 1 and 10 to 1, respectively, together with e, siliceous cete lyst, at a temperature between 100 enoi 350 C. and then separating orthcand pare-cyclohexylphenois therefrom.

11. The method of making orthoend pare-cyclohexylphenols conjointly, which comprises reacting phenol with cyclohexeiie under super-atmospheric pressure, at a temperature between 100 and 350 C. and in the presence of a siliceous'catelyst, said reactants being employed in the ratio of from 1,5 to 10 chemical equivalents of phenol for each chem cal equivalent of cyclohexene.

12. The method of melting cyclohexyh phenols, which comprises adding c clohexeiriic source-materiel to phenol in which letter there is included it siliceous csteiyst eiicl which is heated to a temperature between 100 and 350 C, agitating the mixture during the reaction, filtering the reaction mixture "from the catalyst, enrl separating cit soel pars-c clohexylphenols from Sitlfil reaction phenols, which comprises adding cyclohexerie phenol in which letter there is incliiclezi I '9 hexyloheno l,

source-materiel in the presence ct siliceous "ce'telysecseperetieg the ortho emit pare cyclohezylphenols from the resctioii mixture cod retum the ortho-prooiict to the p 10. The recess of mowing pore-cyclohexylphenci, which comprises reacting phenol with cvclohexeoe source-materiel at e temperetiirehetween175 end 350 0. cool in the presence of e siliceous catalyst, seperetii1 orthocoal pere-cyclohexylphenols from e crude reectioii mixture end returning seitl ortho compound. to the process.

17.. The process of melding pore-cyclohexylphenol, which comprises reacting phenol tirith'cyclohexeiie in the presence of e, siliceous cetellyst, sepsretiog orthoand pere-cyclohexylphenols from the crude reaction mixture encl returning seid ortho compound to the process.

18. The process of melting pare-cycloliexylphenol, which comprises reacting phenol with cyclohexene end cyclohexylphenol at e temperature between 1l5 and 350 0. e110 in the presence of e siliceous catalyst, frectionelly tlistiliirig the crude reectioii mixture to sepercte othoand pore-.

cyclohexylphenels therefrom, and retomirig seid ortho compound to the process,

19. In e process of the hereiio. described neture for melting pere-cyciohexylphenol by reacting phenol with cyclohexemc scurwmeteriel, the stepo'f returningorthocyclo hexyipheool formed in the reoctioii to the process.

20. lo process of meiririg' perm-cyclohezrylpheool, converting ortho-cyciohexylhenol into the corresponding pare com- 50 pooiio'i hy heetiii the former to e terneiice o siliceous catalyst.

zill. methoil oi rookie ortho-, rziete-, not cori] omtly,

pcre-cyclohexylpheno s cich comprises reacting phenol with e cyclosouree-msterisl at e temperature he- W083i 100 350 UL encl in they presence :l' e siliceo'es catalyst, cool separating ortho, -iete pere-cyclolieizylpheeol from the section 221 The methcrl of making so ortho cycloiier ylphenol en cl its pore-isomer coiijoiiitly, which comprises reacting c. phenol, liming hyclregeii or sol) stitiieot selected from the group consisting hyclrccerhoio, ell-sexy, eryloxy one circllroxy solostitoeiits, cyclohexeiie curler super-atmospheric pressure, st e, tempereture between 175 end 350 Q, end is the pres ence of e, siliceous catalyst Signeii lay us this 20th .tlsy of Qctoher,

- o esrr ros. i recite.

between emi 350 C; in the pres- GERTIFECATE 0F comcmfl.

Patent'Na 1,917, 23. July 11, was.

EDGAR Q, ERETTQN, ET? AL.

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